CN102549059A - Anaerobically curable compositions - Google Patents

Anaerobically curable compositions Download PDF

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CN102549059A
CN102549059A CN2010800461489A CN201080046148A CN102549059A CN 102549059 A CN102549059 A CN 102549059A CN 2010800461489 A CN2010800461489 A CN 2010800461489A CN 201080046148 A CN201080046148 A CN 201080046148A CN 102549059 A CN102549059 A CN 102549059A
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methyl
compsn
ester
benzoxazine
vinylformic acid
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CN102549059B (en
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S·阿塔尔瓦洛
Q·朱
D·P·伯基特
M·怀尔
D·马伦
L·麦加里
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Henkel IP and Holding GmbH
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Henkel Loctite Ireland Ltd
Henkel Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Abstract

The present invention relates to anaerobically curable compositions containing a benzoxazine component and which demonstrates resistance to elevated temperature conditions and/or accelerated cure speed.

Description

The anaerobic curing compsn
Technical field
The present invention relates to comprise the anaerobic curing compsn of benzoxazine component, and it shows to the resistivity of hot conditions and/or the curing speed of acceleration.
Background technology
Generally speaking the anaerobism binding compsns is known.For example exist Handbook of Adhesive Technology, 29,467-79, A.Pizzi and K.L.Mittal, editor, Marcel Dekker, Inc., in (1994) one books of New York, " the Anaerobic Adhesives " that R.D.Rich write, and the reference of quoting.They are widely used and new purposes is continually developed out.
Conventional anaerobic adhesive comprises acrylate monomer and the peroxy initiator and the suppressor factor composition of free redical polymerization usually.Generally, this type anaerobism binding compsns also comprises promoter component, and this component is quickened the curing of compsn.
Through adding specific additive, a lot of tackiness agents especially anaerobic adhesive have been endowed the resistivity to high temperature degradation.For example, United States Patent(USP) No. 3,988,299 (Malofsky) relate to a kind of heat-curing composition with improved thermodynamic behaviour, and it comprises specific acrylate monomer and maleimide compound.
L.J.Baccei and B.M.Malofsky, at L-H, Lee edits, and Plenum publishing company (1984) publishes Adhesive Chemicals589-601; " the Anaerobic Adhesives Containing Maleimides Having Improved Thermal Resistance " that deliver reported maleimide---specifically; N-phenylmaleimide, the reaction product of m-phenylenedimaleimide and diamino phenylmethane and (methylenedianiline) bismaleimides---can be used to strengthen the thermotolerance of anaerobic adhesive, but this anaerobic adhesive completely solidified under at least 150 ℃ of temperature.
Cause it to have resistivity though in anaerobic adhesive compsns, add this type maleimide compound, thereby the reaction product with acceptable ability is provided, but still the alternate compound that is included in the said prescription is found in expectation thermal destruction.
Henkel Corp. designed in the past some to thermal destruction have the enhanced resistivity anaerobic adhesive compsns.For example, United States Patent(USP) No. 6,342,545 (Klemarczyk) are open and require a kind of radically curing compsn of protection, and its radical-cured reaction product at high temperature shows enhanced viscosity and reaches the resistivity to thermal destruction.This cured compositions under anaerobic comprises (a) (methyl) propenoate composition; (b) the potential imidazoles (latent imidazole) of heat resist property reagent is given in the conduct of effective content; (c) radically curing-induce composition, for example anaerobic curing-induce composition.Said potential imidazoles is the adduct that obtains through the compound with reactive hydrogen and uncle's amino group, epoxy compounds and carboxylic acid anhydride reaction.And the reagent of giving heat resist property is selected from the combination of Methylimidazole, benzoyl-imidazoles, phenacyl-imidazoles, phthalyl diimidazole and above-mentioned substance.
United States Patent(USP) No. 6150479 (Klemarczyk) is also open and require to have protected a kind of radically curing compsn, the radically curing reaction product of this radically curing compsn at high temperature to show the viscosity of raising and to the resistivity of thermal destruction.This cured compositions under anaerobic comprises: (a) (methyl) acrylate component; (b) have the coreagent component of a fixed structure, its example comprises acrylic acid epoxy citronellyl acrylate, methylacrylic acid epoxidation citronellyl acrylate, vinylformic acid cyclohexenyl methyl esters (cyclohexenyl methanol acrylate), methylacrylic acid cyclohexenyl methyl esters, methylacrylic acid epoxidized cyclohexene base methyl esters, vinylformic acid dihydro Dicyclopentadiene (DCPD) ester, acrylic acid epoxy dihydro Dicyclopentadiene (DCPD) ester, methacrylic acid dihydride Dicyclopentadiene (DCPD) ester, methylacrylic acid epoxidation dihydro Dicyclopentadiene (DCPD) ester, epoxidation 2-vinylformic acid, 2-[(3a, 3; 4,5,6; 7,7a-six hydrogen-4,7-endo-methylene group-1H-indenyl) oxygen] ethyl ester, epoxidation-2-vinylformic acid, 2-methyl-2-[(3a; 3,4,5; 6; 7,7a-six hydrogen-4,7-endo-methylene group-1H-indenyl) oxygen] ethyl ester and their combination; (c) radically curing-induce composition, for example anaerobic curing-induce composition.Here, in the compsn existence of coreagent provide have improved viscosity and thermal destruction resistivity the radically curing reaction product.Also can comprise the reagent of giving heat resistance in the compsn; For example be selected from imdazole derivatives (the for example combination of benzoyl-imidazoles, Methylimidazole, benzoyl-Methylimidazole, phthalyl diimidazole and above-mentioned substance), potential imidazoles, and through making the adduct of the compound, epoxy compounds and the carboxylic acid anhydride reaction acquisition that have active hydrogen and uncle's amino group in the molecule.
Benzoxazine itself has the characteristic of high glass transition temperature, good electrology characteristic (for example specific inductivity) and low combustible usually by bibliographical information,
The blend of epoxy resin and benzoxazine is known.Be found in, for example USP 4,607,091 (Schreiber), 5,021,484 (Schreiber), 5,200,452 (Schreiber), and 5,445,911 (Schreiber).And the ternary blends of epoxy resin, benzoxazine and resol also is known.Be found in United States Patent(USP) No. 6207786 (Ishida), reach S.Rimdusit and H.Ishida and exist Polymer, 41, " Development of new class of electronic packaging materials based on ternary system of benzoxazine, epoxy, the and phenolic resin " that 7941-49 (2000) delivers.Also being found in United States Patent(USP) No. 6620905 (Musa) and application publication number is the U.S. Patent application of US 2004/0123948 (Dershem).
United States Patent(USP) No. 4,569,976 (Zimmermann) are in the situation of the improved redox curing system of the acryloid cement that has been in the news, and at the 4th row, 44-54 is capable to be pointed out:
Suitably the ring has a ring hetero atom in the beta position a substituent thiourea fused ring structure (also described 2 - thiourea derivatives), including benzofuran, benzothiophene, benzoxazole isobutyl, benzyl pyrazole, benzisoxazole, benzoxazole, 1,4 - phenyl piperazine carbazole (benzpyrone), quinoline, tetrahydroquinoline, isoquinoline, tetrahydroisoquinoline, cinnoline, quinazoline, naphthalene, pyridine, benzoxazine and the like.The acvator that preferably has the condensed ring structure comprises 2-quinoline thiocarbamide, 1-isoquinoline 99.9 thiocarbamide and 2-naphthyridines thiocarbamide.
Although prior art is like this, still has lasting effort to improve the for example thermal property of the reaction product of anaerobic curing compsn of radically curing compsn, and provide alternative technology to improve the curing speed of these compsns.
Summary of the invention
Anaerobic curing compsn of the present invention comprises (a) (methyl) acrylic component; (b) anaerobic curing-induce composition; And (c) benzoxazine composition, for example the position 2 with respect to the benzoxazine nitrogen-atoms does not have substituent benzoxazine.That is to say that the carbon atom that is connected with the benzoxazine nitrogen-atoms desirably has two Wasserstoffatomss.
The present invention also provides preparation and has used the method for the reaction product of anaerobic curing compsn of the present invention and anaerobic curing compsn of the present invention.
Can more completely understand the present invention through reading " detailed Description Of The Invention " and illustrative example thereafter.
Description of drawings
Fig. 1 has described embodiment in the table 1 and has numbered the compsn Strength Changes figure (recording under the breakaway torque) in time that 1-8 describes, and its data are listed in table 2.
Detailed Description Of The Invention
Anaerobic curing compsn of the present invention comprises (a) (methyl) acrylate component; (b) anaerobic curing-induce composition; And (c) there is not substituent benzoxazine composition with respect to the position 2 of benzoxazine nitrogen-atoms.That is to say that each carbon atom that links to each other with the benzoxazine nitrogen-atoms respectively carries two Wasserstoffatomss.
(methyl) acrylate component is optional from wide variety of materials, for example, and by H 2C=CGCO 2R 1Those of expression, wherein G can be hydrogen, halogen or contains 1 alkyl group to about 4 carbon atoms, and R 1Optional Zi containing 1 alkyl, naphthenic base, thiazolinyl, cycloalkenyl group, alkaryl, aralkyl or aromatic yl group to about 16 carbon atoms; Wherein any one all can randomly be replaced or be interrupted by silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbonic ether, amine, acid amides, sulphur, sulphonate, sulfone and resemblance thereof with playing by ear.
Be suitable for other (methyl) acrylate monomer of the present invention and comprise multi-functional (methyl) acrylate monomer, for example, but be not limited only to; Two-or (methyl) propenoate of three-functional group like two (methyl) polyalkylene glycol acrylate ester, the acrylic acid tetrahydrofuran ester of (methyl) vinylformic acid and two (methyl), (methyl) vinylformic acid hydroxypropyl ester (" HPMA "); Two (methyl) vinylformic acid pinakon ester, trimethylolpropane tris (methyl) propenoate (" TMPTMA "), dimethacrylate glycol ether ester; Dimethacrylate triethyleneglycol ester (" TRIEGMA "), dimethacrylate Tetraglycol 99 ester, dimethacrylate DPG ester; Dimethacrylate two (1, the 5-pentanediol) ester, diacrylate Tetraglycol 99 ester; Tetramethyl-vinylformic acid double glyceride, dimethacrylate tetramethylene ester, dimethacrylate ethyl; Diacrylic acid pentyl diol ester; Viscoat 295, and the list of bisphenol-A (methyl) propenoate and two (methyl) propenoate, for example (methyl) vinylformic acid ethoxylation bisphenol-A ester (" EBIPMA "); And list (methyl) propenoate and the acrylic acid ester of two (methyl) of bisphenol-f, for example (methyl) vinylformic acid ethoxylation bisphenol-f ester.
Also have other (methyl) acrylate monomer to can be used for the present invention; Comprise organosilicon (methyl) acrylate group (" SiMA "), for example those are at United States Patent(USP) No. 5,605; Instruction and requirement are protected among 999 (Chu), and its disclosure method is by reference introduced among the application.
Certainly, also can use the combination of these (methyl) acrylate monomers.
Based on the composition total weight meter, (methyl) propenoate composition should occupy about 10 weight % of compsn to about 75 weight %, and for example about 50 weight % are to about 70 weight %.
The benzoxazine component that can comprise in the compsn of the present invention is used for improving resistivity and/or the acceleration curing speed to hot conditions.Said benzoxazine composition comprises
Figure BDA0000152857980000051
Wherein o is 1-4, and X is selected from direct key (when o is 2), alkyl (when o is 1), alkylidene group (when o is 2-4), carbonyl (when o is 2), sulfydryl (when o is 1), thioether (when o is 2), sulfoxide (when o is 2) or sulfone (when o is 2), and R 1Be aryl, or
Figure BDA0000152857980000052
Wherein p is 2; Y is selected from xenyl (when p is 2), ditan (when p is 2), the different propane of phenylbenzene (when p is 2), diphenylsulfide (when p is 2), diphenyl sulfoxide (when p is 2), sulfobenzide (when p is 2) or diphenylketone (when p is 2), and R 4Be selected from hydrogen, halogen, alkyl or alkenyl.
In more detail, benzoxazine component can comprise one or more in the following material:
Figure BDA0000152857980000053
Figure BDA0000152857980000061
Wherein X is selected from direct key, CH 2, C (CH 3) 2, C=O, S, S=O or O=S=O, and R 1, R 2, and R 3Be identical or different aryl, R 4Be selected from hydrogen, alkyl, thiazolinyl or aryl.
Perhaps, benzoxazine component comprises following material:
Figure BDA0000152857980000071
Wherein X is selected from direct key, CH 2, C (CH 3) 2, C=O, S=O, O=S=O or S, R 1And R 2Identical or different, and be selected from methyl, ethyl, propyl group or butyl.
More specifically, benzoxazine component comprises following material:
Figure BDA0000152857980000072
R wherein 1And R 2Identical or different, and they are selected from methyl, ethyl, propyl group and butyl, though in a special preferred examples R 1And R 2It all is aryl.
The special instance of bifunctional benzoxazine comprises:
Figure BDA0000152857980000073
Benzoxazine also can be the simple function group benzoxazine.For example, the simple function group benzoxazine can comprise:
Figure BDA0000152857980000082
Wherein R is selected from C 1-40Alkyl, C 2-40Thiazolinyl, wherein each is all randomly by the one or more replacements among O, N, S, C=O, COO and the NHC=O or be interrupted and C 6-20Aryl; M is 0-4, R 1-R 5Be independently selected from C 1-40Alkyl, C 2-40Thiazolinyl, C 1-40Alkoxyl group, C 2-40Alkene oxygen base, wherein each is all randomly by the one or more replacements among O, N, S, C=O, COOH and the NHC=O or be interrupted and C 6-20Aryl, and R 1-R 5In have one at least.
Perhaps, the simple function group benzoxazine can comprise:
Figure BDA0000152857980000083
Wherein R is an alkyl, for example methyl, ethyl, propyl group and butyl, perhaps one, a plurality of or all instead positions all have or do not have substituent aryl, R 4Be selected from hydrogen, halogen, alkyl and thiazolinyl, for example wherein R is aromatic nucleus and R 4Be H.
The representational example of described simple function group benzoxazine comprises:
Figure BDA0000152857980000091
Figure BDA0000152857980000101
The purpose that comprises benzoxazine in the thing combined according to the invention, based on the gross weight of compsn, benzoxazine component accounts for the amount of about 0.01 weight % of compsn to about 60 weight %, and for example about 0.10 weight % is to the amount of about 30% weight.In the time that benzoxazine is used to improve the resistivity to hot conditions, the consumption of benzoxazine component should be 5 weight % to 60 weight %, for example about 10-15 weight %; When benzoxazine is used for forming to unite with anaerobic curing-induce using when quickening curing speed, the consumption of benzoxazine component should be 0.01 weight % to 5 weight %, and for example about 0.01 weight % is to 2.5 weight %.
Induce and quicken the desirable anaerobic curing of present composition solidified-induce composition (or anaerobic curing system) and can comprise the stablizer of asccharin, toxilic acid and for example quinones, for example naphthoquinones and anthraquinone.By convention, this type anaerobic curing-induce composition also to comprise the toluene amine, N for example, N-diethylammonium-right-monomethylaniline (" DE-p-T ") and N, N-dimethyl--neighbour-monomethylaniline (" DM-o-T ") and pyrodin (" APH ").Yet above-mentioned materials is optional among the present invention.It is thus clear that for example United States Patent(USP) No. 3,218,305 (Krieble), 4,180,640 (Melody), 4,287,330 (Rich) and 4,321,349 (Rich).Among the present invention, benzoxazine component can be used for substituting part or all of Tolylamine.
Compsn of the present invention also can comprise other conventional component, and metal catalyst for example is like iron and copper.In the anaerobism prescription that only contains a part (one-part), do not hope to occur metal catalyst (therefore using sequestrant to precipitate metal) usually.In containing the anaerobism prescription of two portions (two-part), metal catalyst can join in that part prescription that does not contain initiator such as peroxy compound.
The many known initiator of Raolical polymerizable can be added in the present composition usually, includes but are not limited to: hydroperoxide, CHP for example, hydrogen peroxide terpene, tertbutyl peroxide (" TBH ") and TBPB tertiary butyl perbenzoate.Other superoxide comprise benzoyl peroxide, dibenzoyl superoxide, 1; 3-two (tert-butyl hydroperoxide sec.-propyl) benzene, diacetyl superoxide, butyl-4; 4-two (tert-butyl hydroperoxide) valerate, to chlorobenzoyl superoxide, Cumene Hydroperoxide 80, tertiary butyl cumene peroxide, TBPB tertiary butyl perbenzoate, two-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl--2; 5-two-tert-butyl hydroperoxide hexane, 2; 5-dimethyl--2,5-two-tertiary butyl-peroxy oneself-3-alkynes, 4-methyl-2, the combination of 2-two-tert-butyl hydroperoxide pentane and above-mentioned substance.
Based on the gross weight meter of compsn, anaerobic curing-induce the usage quantity of composition to can be about 0.1 weight % to 10 weight %, for example about 1 weight % is to 5 weight %.
Other components have been included in the physical property that changes curable compositions or its reaction product in traditional anaerobic curing compsn.For example; Thickening material, non-reactive softening agent, filler, intensifier (for example elastomerics and rubber, coreagent; Maleimide for example), and other known additives can add in the said compsn, as long as those skilled in the art think to do like this need.
The present invention also provides the preparation and the method for use of the reaction product of anaerobism binding compsns of the present invention and said compsn.
The ordinary method preparation that compsn involved in the present invention can be known by one of skill in the art.For example, the component of the present composition can be any easily order mix, this order and component due effect and function in compsn are consistent and get final product.Use the conventional hybrid technology of known device may be utilized.
Compsn involved in the present invention can be used for various matrix, realizes the benefit and the advantage of expectation described in the invention.For example, suitable matrix can be made up of steel, brass, copper, aluminium, zinc, glass and other metals and alloy, pottery and thermosetting material.The beneficial characteristics that compsn of the present invention has makes it be suitable for liner and Application of composite.Compositions table of the present invention reveals steel and the good especially cohesive strength of aluminium.Use suitable priming paint can strengthen the solidification rate of the present composition in selected stromal surface.It is thus clear that, for example, United States Patent(USP) No. 5,811,473 (Ramos).
The present invention also provides a kind of method by anaerobism binding compsns preparation feedback product of the present invention; The step of this method is included in the stromal surface applying said compositions of needs and said compsn is placed the anaerobic environment certain hour, and this time enough makes compsn solidify.
Can find out by foregoing description of the present invention, purposes widely is provided obviously.Following providing of embodiment is merely illustration purpose, rather than structure limits instruction of the present invention by any way.
Embodiment
Embodiment
Synthetic embodiment
Benzoxazine, for example the benzoxazine of single functional group refers to PA-BOZ here, can be prepared by following method:
With aniline (93g, 1.0mol), Paraformaldehyde 96 (60.0g, 2.0mol), phenol (94.0g, 1.0mol) and toluene (2000ml) put into and have churned mechanically 5000 milliliter of three neck round-bottomed flask.The Dean Stark moisture receptor of being furnished with condensing surface is used for collecting the moisture that this reaction generates.Mixture, continues to stir to refluxing at the 4h internal heating simultaneously.Total is collected the water of 36ml (2.0mol).Reaction mixture is cooled to room temperature, and passes through silica gel thin-layer.Then, utilize rotary evaporation to remove solvent, residual liquid blew 4 hours with nitrogen.Change aniline the right-ethyl-aniline of equimolar amount into, utilize above-mentioned steps to make Et-PA-BOZ.N-ethanoyl-right-phenyl the diamines that aniline is changed into equimolar amount utilizes above-mentioned steps to make AM-PA-BOZ.Right-ethyl-the aniline that aniline is changed into equimolar amount utilizes above-mentioned steps to make Met-PA-BOZ.
The diallyl bisphenol benzoxazine can be through 51.0g (165.4mmol) 2 in being contained in the 500ml beaker at room temperature, stirs in 2 '-diallyl bisphenol to add 30.8g (330.7mmol) aniline and prepare.The mixture that is stirring subsequently is positioned in the ice bath and is cooled to and is lower than 5 ℃.Under agitation, Paraformaldehyde 96 (19.9g; 663.3mmol) in 20 minutes by part adding.Then, mixture rises to room temperature and stirred 15 minutes.Progressively be warming up to 80 ℃ and stirred 1 hour then.Then be warming up to 120 ℃ and stirred 2 hours.Then be dissolved in crude product mixture in the chloroform and to utilize 4N NaOH to give a baby a bath on the third day after its birth several all over coming purifying all over washing with deionized water subsequently.Remove chloroform through rotatory evaporator then and obtain required product.Said process is at people such as K.S.Santhosh Kumar " Bis allyl benzoxazine:Synthesis, polymerisation and polymer properties ", Eur.Polym.J., 43, the existing report of 2504-2514 (2007).
Utilize BOZ promotor preparation anaerobic adhesive
Prepared eight kinds of compsns, every kind all comprises (methyl) propenoate composition (comprising PEGMA) and other components, lists in below table 1 with weight percent:
Table 1
At first, under room temperature mechanical mixing condition, add said each an amount of component and prepare compsn.
The mixed suitable time of each component reaches dissolving and/or the dispersion for the situation that contains solid ingredient.With the preparation of above-mentioned formation through covering beaker to guarantee keeping air bag to store between preparation surface and the lid to be used for further use.
Preparation of the present invention shows the storage property of passing by in time in the open container at room temperature.
Use and envrionment temperature
Contain the curing of the anaerobic adhesive of BOZ promotor
Be applied to the degreasing soft steel nuts and bolt assembly twice of five cover 3/8x16 according to the sample ligand goods of method for preparing, then make it at room temperature solidify about 0.25,0.5,1,1.5,2,4 and 24 hour time.After set time, utilize breaking tenacity and ys (prevail strength) that fastening piece is assessed, assessment data such as following table 2 are with shown in Figure 1:
Table 2
Fracture/the surrender (N.m) of degreasing steel nuts and bolt
Figure BDA0000152857980000141
These data show, the function that compsn of the present invention (sample number into spectrum 2-7) is used on matrix when solidifying at room temperature is similar based on (methyl) acrylic acid anaerobic adhesive with tradition.In fact, compare with the sample No.1 that does not add promotor, even compare with containing the sample No.8 of diethylammonium-right-Tolylamine with the dimethyl-o-toluidine combination, compositions table of the present invention reveals the curing speed of increase.
With the prescription of BOZ as the anaerobic adhesive of toughner
At first, we have assessed the LOCTITE272 that contains with not containing the benzoxazine component of different levels and have confirmed the relatively hot intensity level.
LOCTITE 272 by the hydrogen phosphide cumene (CAS No.80-15-9) of the hydroxyalkyl methacrylate (CAS No.27813-02-1) of the maleimide resin (CAS No.3006-93-7) of the aromatic dimethyl propenoate (CAS No.24448-20-2) of 60-100%, 10-30%, 1-5%, 1-5%, 1-5% silicon-dioxide (amorphous, gas phase, crystal type free) (CASNo.112945-52-5), and 0.1-1%APH (CAS No.114-83-0) forms.
In the following Table 3, LOCTITE 272 is used as contrast, and is known as the benzoxazine preparation that sample No.9. sample Nos.10-11 uses LOCTITE 272 and following demonstration amount.
Table 3
Sample No. Benzoxazine
9 0
10 30
11 60
The benzoxazine composition here is the mixing of the following material of weight ratio 60/40:
Wherein R is an aromatic nucleus, and R 4Be H.
With reference to following table 4-6; Can find out; After sample No.9 (no benzoxazine) is applied to Steel Bolt and nut, at room temperature solidify the breaking tenacity that shows 10.7N.m after time of 24 hours, and the thermal destruction intensity after under 150 ℃ of temperature 24 hours is merely 9.4N.m.The retention rate that this reduction of hot strength is interpreted as hot strength is 87%.
By contrast, at room temperature solidify the breaking tenacity that shows 11.0N.m and 8.7N.m respectively of (each all contains benzoxazine) of sample 10 and 11 after 24 hours, be respectively 13.0N.m and 19.4N.m 150 ℃ of thermal destruction intensity after following 24 hours.The increase of this hot strength is interpreted as the hot strength retention rate and is respectively 118% and 223%.Therefore, with the intensity that keeps, sample No.9 shows 13% reduction after the section 150 ℃ of preset times, and sample Nos.10 and 11 shows significant increase after the section 150 ℃ of preset times, and this has shown that benzoxazine plays a positive role to sample.
Table 4
Figure BDA0000152857980000161
Table 5
Figure BDA0000152857980000162
Table 6
Figure BDA0000152857980000163

Claims (12)

1. anaerobic curing compsn comprises:
A) (methyl) acrylate component;
B) anaerobic curing system; With
C) benzoxazine component.
2. the described compsn of claim 1, wherein said benzoxazine component comprises:
Figure FDA0000152857970000011
Wherein o is 1-4, and X is selected from direct key (when o is 2), alkyl (when o is 1), alkylidene group (when o is 2-4), carbonyl (when o is 2), sulfydryl (when o is 1), thioether (when o is 2), sulfoxide (when o is 2) and sulfone (when o is 2), and R 1Be aryl, or
Wherein p is 2; Y is selected from xenyl (when p is 2), ditan (when p is 2), the different propane of phenylbenzene (when p is 2), diphenylsulfide (when p is 2), diphenyl sulfoxide (when p is 2), sulfobenzide (when p is 2) and diphenylketone (when p is 2), and R 4Be selected from hydrogen, halogen, alkyl and thiazolinyl.
3. the described compsn of claim 1, wherein said benzoxazine component comprises one or more in the following material:
Figure FDA0000152857970000021
Figure FDA0000152857970000031
Wherein X is selected from direct key, CH 2, C (CH 3) 2, C=O, S, S=O and O=S=O, and R 1, R 2, and R 3Be identical or different aryl, and R 4Be selected from hydrogen, alkyl, thiazolinyl and aryl.
4. the described compsn of claim 1, wherein said benzoxazine component comprises:
Figure FDA0000152857970000032
Wherein X is selected from direct key, CH 2, C (CH 3) 2, C=O, S=O and O=S=O, S, and R 1And R 2Be identical or different aryl.
5. the described compsn of claim 1, wherein said benzoxazine component comprises:
Figure FDA0000152857970000033
R wherein 1And R 2Be identical or different aryl.
6. the described compsn of claim 1, wherein said (methyl) acrylate component is used H 2C=CGCO 2R 1Expression, wherein G is selected from H, halogen and contains 1 alkyl to about 4 carbon atoms, R 1Be selected from and contain 1 alkyl, naphthenic base, thiazolinyl, cycloalkenyl group, alkaryl and aryl to about 16 carbon atoms, its by or a member of not being selected from the group that silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbamate, amine, acid amides, sulphur, sulphonate and sulfone form replace or be interrupted.
7. the described compsn of claim 1, wherein said (methyl) acrylate component is selected from organosilicon (methyl) propenoate, two (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid bisphenol-A ester, (methyl) vinylformic acid ethoxylation bisphenol-A ester, (methyl) vinylformic acid bisphenol-f ester, (methyl) vinylformic acid ethoxylation bisphenol-f ester, (methyl) vinylformic acid tetrahydrofuran ester and two (methyl) vinylformic acid tetrahydrofuran ester, (methyl) vinylformic acid hydroxypropyl ester, two (methyl) vinylformic acid pinakon ester and trimethylolpropane tris (methyl) propenoate.
8. compsn as claimed in claim 1, wherein said benzoxazine component is as toughner.
9. compsn as claimed in claim 1, wherein said benzoxazine component is as promotor.
10. the reaction product of the said compsn of claim 1.
11. the method by anaerobic curing preparation of compositions reaction product comprises following steps:
The described anaerobic curing compsn of claim 1 is applied to required stromal surface, and
Said compsn is exposed in the anaerobic environment through being enough to make the compsn solidified time.
12. a structure, be included in two the pairing matrix between by the described compsn of claim 1 form bonding.
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